Active agent combinations

ABSTRACT

The novel active compound combinations of
         extracts from seeds of the neem tree and   the active compounds of groups (B) to (F) listed in the description
 
have very good insecticidal and acaricidal properties.

This application is a Divisional application of U.S. application Ser.No. 13/097,508, filed Apr. 29, 2011, which is a Divisional of U.S.application Ser. No. 10/432,979, filed Oct. 3, 2003, now U.S. Pat. No.7,955,609 issued Jun. 7, 2011, which is a National Stage ofPCT/EP01/13340, filed Nov. 19, 2001, which claims priority to GermanApplication 10059606.1, filed Dec. 1, 2000. All of these are herebyincorporated by reference in their entireties.

The present invention relates to novel active compound combinationswhich comprise, firstly, known extracts from seeds of the neem tree and,secondly, further known pesticidally active compounds, and which havevery good insecticidal and acaricidal properties.

It is already known that extracts from the seeds of the neem tree haveinsecticidal properties (cf. “Römpp Chemie Lexikon”, 9^(th) edition,page 2954, Georg Thieme Verlag, Stuttgart-New York, 1991). The activityof this substance is good; however, it is sometimes unsatisfactory atlow application rates.

It is furthermore known that numerous pyrethroids, carbamates,phosphoric acid derivatives and heterocycles can be used for controllinganimal pests such as insects and undesirable acarids (cf. WO 93-10 083;DE-A 2 717 040; Farm Chemicals Handbook 1998, C 328; EP-A 0 161 019 andEP-A 0 049 977). However, the activity of these substances is likewisenot always satisfactory at low application rates.

It has now been found that the novel active compound combinationscomprising

-   A) extracts from seeds of the neem tree-   and-   B) an active compound from the group of the pyrethroids, consisting    of    -   (1) cypermethrin,    -   (2) deltamethrin,    -   (3) permethrin,    -   (4) natural pyrethrum,    -   (5) fenpropathrin,    -   (6) cyfluthrin,    -   (7) beta-cyfluthrin and    -   (8) lambda-cyhalothrin,-   or-   C) an active compound from the group of the carbamates, consisting    of    -   (9) butocarboxim,    -   (10) pirimicarb,    -   (11) propoxur and    -   (12) methiocarb,-   or-   D) a phosphoric acid derivative from the group consisting of    -   (13) isazophos and    -   (14) dimethoate,-   (E) an active compound from the group of the nicotinyls or    neonicotinyls consisting of    -   (15) imidacloprid,    -   (16) thiacloprid,    -   (17) thiamethoxam,    -   (18) acetamiprid and    -   (19) clothianidin,-   or-   (F) an active compound from the group consisting of    -   (20) abamectin,    -   (21) diflubenzuron,    -   (22) buprofezin,    -   (23) triflumuron,    -   (24) diafenthiuron,    -   (25) fipronil,    -   (26) spinosad,    -   (27) pymetrozine,    -   (28) cyromazine,    -   (29) dicyclanil,    -   (30) bifenazate,    -   (31) hexathiazox,    -   (32) tebufenpyrad,    -   (33) pyridaben,    -   (34) the ketoenol derivative (I) of the name        3-(2,4-dichlorophenyl)-4-(1,1-dimethyl-propyl-carbonyloxy)-5-spiro-cyclohexyl-3-dihydrofuran-2-one    -   and    -   (35) the ketoenol derivative (II) of the name        3-(2,4,6-trimethylphenyl)-4-(2,2-dimethyl-propyl-carbonyloxy)-5-spiro-cyclopentyl-3-dihydrofuran-2-one        have very good insecticidal and acaricidal properties.

Surprisingly, the insecticidal and acaricidal activity of the activecompound combinations according to the invention is considerably higherthan the sum of the activities of the individual active compounds. Thus,an unforeseeable, true synergistic effect is present, and not just anaddition of activities.

In the present case, extracts from seeds of the neem tree are to beunderstood as meaning all customary products which can be isolated fromseeds of the neem tree by extraction or squeezing and which containsubstantial quantities of azadirachtin. These products includeazadirachtin itself.

Various extracts of seeds of the neem tree and azadirachtin itself arealready known (cf. “The Pesticide Manual” 11^(th) edition, British CropProtection Council 1997, No. 36 and also “Römpp Chemie Lexikon”, 9^(th)edition, page 2954, Georg Thieme Verlag, Stuttgart-New York, 1991).

The insecticidally and acaricidally active components which are presentin the active compound combinations according to the invention inaddition to the extracts from the seeds of the neem tree are likewiseknown. The following substances are specifically described in “ThePesticide Manual”, 11^(th) edition, British Crop Protection Council,1997:

 (1) cypermethrin under No. 185,  (2) deltamethrin under No. 204,  (3)permethrin under No. 561,  (4) natural pyrethrum under No. 622,  (5)fenpropathrin under No. 312,  (6) cyfluthrin under No. 176,  (7)beta-cyfluthrin under No. 177,  (8) lambda-cyhalothrin under No.[lacuna]  (9) butocarboxim under No.  95, (10) pirimicarb under No. 583,(11) propoxur under No. 610, (12) methiocarb under No. 482, (13)isazophos under No. 429, (14) dimethoate under No. 243, (15)imidacloprid under No. 418, (18) acetamiprid under No.  5, (20)abamectin under No.  1, (21) diflubenzuron under No. 231, (22)buprofezin under No.  92, (23) triflumuron under No. 739, (24)diafenthiuron under No. 208, (25) fipronil under No. 323, (26) spinosadunder No. 754, (27) pymetrozine under No. 615 (28) cyromazine under No.191, (29) dicyclanil under No. 244, (30) bifenazate under No. 193, (31)hexathiazox under No. 401, (32) tebufenpyrad under No. 680 and (33)pyridaben under No. 624.

The other of the abovementioned active compounds are described in thefollowing publications:

(16) thiacloprid EP-A-0 235 725 (17) thiamethoxam EP-A 0 580 533, (19)clothianidin EP-A 0 376 279, (34) ketoenol derivative (I) EP-A 0 528 156and (35) ketoenol derivative (II) EP-A 0 528 156.

In addition to the extract from the seeds of the neem tree, the activecompound combinations according to the invention comprise at least oneof the active compounds from groups (B) to (F). Additionally, they maycomprise further insecticidally and/or acaricidally active components.

The synergistic effect is particularly pronounced if the activecompounds are present in the active compound combinations according tothe invention in certain weight ratios. However, the weight ratios ofthe active compounds in the active compound combinations can be variedwithin a relatively wide range. In general,

from 0.02 to 20 parts by weight, preferably from 0.3 to 17 parts byweight, of active compound from group (B),

from 1 to 80 parts by weight, preferably from 1.5 to 70 parts by weight,of active compound from group (C),

from 1 to 60 parts by weight, preferably from 3 to 50 parts by weight,of active compound from group (D),

fro 0.2 to 50 parts by weight, preferably from 0.3 to 40 parts byweight, of active compound from group (E) and

from 0.2 to 60 parts by weight, preferably from 0.3 to 50 parts byweight, of active compound from group (F)

are present per part by weight of extract from seeds of the neem tree.

The active compound combinations according to the invention are suitablefor controlling animal pests, preferably arthropods and nematodes, inparticular insects and arachnids, which are encountered in agriculture,in gardening, in forests, in the protection of stored products and ofmaterials and in the hygiene sector. They are active against normallysensitive and resistant species and also against all or some stages ofdevelopment. The abovementioned pests include:

From the order of the Isopoda, for example, Oniscus asellus,Armadillidium vulgare and Porcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus.

From the order of the Chilopoda, for example, Geophilus carpophagus andScutigera spec.

From the order of the Symphyla, for example, Scutigerella immaculata.

From the order of the Thysanura, for example, Lepisma saccharina.

From the order of the Collembola, for example, Onychiurus armatus.

From the order of the Blattaria, for example, Blatta orientalis,Periplaneta americana, Leucophaea maderae and Blattella germanica.

From the order of the Orthoptera, for example, Acheta domesticus,Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplusdifferentialis and Schistocerca gregaria.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Reticulitermes spp.

From the order of the Anoplura, for example, Phylloxera vastatrix,Pemphigus spp., Pediculus humanus corporis, Haematopinus spp. andLinognathus spp.

From the order of the Mallophaga, for example, Trichodectes spp. andDamalinea spp.

From the order of the Thysanoptera, for example, Frankliniellaoccidentalis, Hercinothrips femoralis, Thrips palmi and Thrips tabaci.

From the order of the Heteroptera, for example, Eurygaster spp.,Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodniusprolixus and Triatoma spp.

From the order of the Homoptera, for example, Aleurodes brassicae,Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicorynebrassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosomalanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp.,Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus,Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphaxstriatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotushederae, Pseudococcus spp. and Psylla spp.

From the order of the Lepidoptera, for example, Pectinophoragossypiella, Bupalus piniarius, Chematobia brumata, Lithocolletisblancardella, Hyponomeuta padella, Plutella maculipennis, Malacosomaneustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrixthurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltiaspp., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestrabrassicae, Panolis flammea, Prodenia litura, Spodoptera spp.,Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyraustanubilalis, Ephestia kuehniella, Galleria mellonella, Tineolabisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoeciapodana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella,Homona magnanima and Tortrix viridana.

From the order of the Coleoptera, for example, Anobium punctatum,Rhizopertha dominica, Acanthoscelides obtectus, Hylotrupes bajulus,Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae,Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis,Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilusspp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchusassimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenusspp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp.,Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor,Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallonsolstitialis and Costelytra zealandica.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis and Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp.,Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp.,Gastrophilus spp., Hyppobosca spp., Lyriomyza spp., Stomoxys spp.,Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibiohortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitiscapitata, Dacus oleae and Tipula paludosa.

From the order of the Siphonaptera, for example, Xenopsylla cheopis andCeratophyllus spp.

From the order of the Arachnida, for example, Scorpio maurus andLatrodectus mactans.

From the order of the Acarina, for example, Acarus siro, Argas spp.,Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptrutaoleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalommaspp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp.,Tarsonemus spp., Bryobia praetiosa, Panonychus spp. and Tetranychus spp.

The active compound combinations according to the invention can be usedwith particularly good results for controlling plant-damaging insectsand acarids, such as, for example, against Tetranychus spp., Panonychuspp., Hemitarsonemus spp., Tarsonemus spp., Brevipalpus spp.,Phylocoptruta spp., Aculus spp., Bryobia spp. and Eriophyes spp.

The fact that the active compound combinations are well tolerated byplants at the concentrations required for controlling insects andacarids permits the treatment of above-ground parts of plants, ofpropagation stock and seeds, and of the soil. The active compoundcombinations according to the invention can be used for foliarapplication or else as seed dressing.

The active compound combinations according to the invention are usuallyemployed in the form of compositions (formulations), for the preparationof which it is possible to use

-   -   the extracts from the seeds of the neem tree in a commercial        preparation or in the form of isolated substances and    -   the active compounds of groups (B) to (F) either as such or in        commercial preparations.

The active compound combinations according to the invention can beconverted into the customary compositions (formulations), such assolutions, emulsions, suspensions, powders, foams, pastes, granules,aerosols, microencapsulations in polymeric compounds and in coatingcompositions for seeds, and ULV formulations.

These formulations are produced in a known manner, for example by mixingthe active compounds or active compound combinations with extenders,that is liquid solvents, liquefied gases under pressure, and/or solidcarriers, optionally with the use of surfactants, that is emulsifiersand/or dispersants, and/or foam formers. If the extender used is water,it is also possible to use, for example, organic solvents as auxiliarysolvents. Essentially, suitable liquid solvents include aromatics, suchas xylene, toluene or alkylnaphthalenes, chlorinated aromatics orchlorinated aliphatic hydrocarbons, such as chlorobenzenes,chloroethylenes or methylene chloride, aliphatic hydrocarbons, such ascyclohexane, or paraffins, for example petroleum fractions, alcohols,such as butanol or glycol and also their ethers and esters, ketones,such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethyl sulphoxide, and also water. Liquefied gaseous extenders orcarriers refer to those liquids which are gaseous at normal temperatureand under atmospheric pressure, for example aerosol propellants, such asbutane, propane, nitrogen and carbon dioxide. Suitable solid carriersare: for example ground natural minerals, such as kaolins, clays, talc,chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, andground synthetic minerals, such as finely divided silica, alumina andsilicates. Suitable solid carriers for granules are: for example crushedand fractionated natural rocks, such as calcite, marble, pumice,sepiolite and dolomite, or else synthetic granules of inorganic andorganic meals, and granules of organic materials such as sawdust,coconut shells, maize cobs and tobacco stalks. Suitable emulsifiersand/or foam formers are: for example nonionic and anionic emulsifiers,such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcoholethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates, or else protein hydrolysates. Suitabledispersants are: for example lignosulphite waste liquors andmethylcellulose.

Tackifiers, such as carboxymethylcellulose and natural and syntheticpolymers, in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, or else naturalphospholipids, such as cephalins and lecithins and syntheticphospholipids, can be used in the formulations. Other possible additivesare mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients, such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations generally comprise between 0.1 and 95 percent by weightof active compounds, preferably between 0.5 and 90%.

In the formulations, the active compound combinations according to theinvention can be present as a mixture with other known active compounds,such as fungicides, insecticides, acaricides and herbicides, and asmixtures with fertilizers or plant growth regulators chelates orsuperabsorbers.

The active compound combinations can be employed as such, in the form oftheir formulations or of the use forms prepared therefrom, such asready-to-use solutions, emulsifiable concentrates, emulsions,suspensions, wettable powders, soluble powders, granules and shapedarticles. The application is carried out in a customary manner, forexample by watering, spraying, atomizing, scattering, spreading, drydressing, wet dressing, liquid dressing, slurry treatment of seeds,incrustation, implantation, injection or by foam application.

When using the active compound combinations according to the invention,the application rates can be varied within a relatively wide range,depending on the type of application. In the treatment of parts ofplants, the application rates of active compound combinations aregenerally between 10 and 3000 g/ha, preferably between 20 and 2000 g/ha.

In the treatment of the soil, the application rates of active compoundcombinations are generally between 10 and 4000 g/ha, preferably between20 and 2000 g/ha.

In the treatment of seeds, the application rates are generally between0.01 and 50 g/kilogram of seed, preferably between 0.05 and 40g/kilogram of seed.

The good insecticidal and acaricidal activity of the active compoundcombinations according to the invention is demonstrated by the examplesbelow. Whereas the individual active compounds have weaknesses in theactivity, the combinations have an activity which exceeds a simpleaddition of activities.

A synergistic effect of insecticides and acaricides is therefore alwayspresent when the activity of the active compound combinations exceedsthe total of the activities of the active compounds when appliedindividually.

The expected activity for a given combination of two active compoundscan be calculated according to S. R. Colby, Weeds 15 (1967), 20-22), asfollows:

If

-   X is the efficacy when applying the active compound A at an    application rate of m g/ha,-   Y is the efficacy when applying the active compound B at an    application rate of n g/ha and-   E is the efficacy when applying the active compounds A and B at    application rates of m and n g/ha,    then

$E = {X + Y - {\frac{X \cdot Y}{100}.}}$

Here, the efficacy is determined in %. 0% means an efficacy whichcorresponds to that of the control, whereas an efficacy of 100% meansthat no infection is observed.

If the actual activity exceeds the calculated value, then the activityof the combination is superadditive, i.e. a synergistic effect exists.In this case, the efficacy which was actually observed must be greaterthan the value for the expected efficacy (E) calculated from the formulagiven above.

The invention is illustrated by the following examples:

Example 1 Trialeurodes Test

To produce a suitable preparation of active compound, a commercialformulation of active compound or active compound combination is mixedwith water until the desired concentration is reached.

Red sage (Lantana camara) which is heavily infested by all stages of thewhitefly (Trialeurodes vaporariorum) is sprayed in intervals of 7 daysin each case with a preparation of active compound at the desiredapplication rate.

Evaluation is carried out 15 days after the second treatment. 100% meansthat all flies have been killed, whilst 0% means that none of the flieshave been killed.

Active compounds, application rates and test results are shown in thetable below.

TABLE 1 Trialeurodes test Application rate of active Active compoundcompound in g/ha Kill rate in % Known: Neem extract*⁾ 30 28.6 (16)thiacloprid 100 72.8 According to the found calc.**⁾ invention Neemextract*⁾ 30 + {close oversize brace} + {close oversize brace} 91.9 80.6(16) Thiacloprid 100 *⁾The neem tree seed extract used is commerciallyavailable under the name Neem-Azal ® (from Terfolio). **⁾found =activity found calc. = activity calculated using Colby's formula

Example 2 Trialeurodes Test

To produce a suitable preparation of active compound, a commercialformulation of active compound or active compound combination is mixedwith water until the desired concentration is reached.

Red sage (Lantana camara) which is heavily infested by the whitefly(Trialeurodes vaporariorum) is sprayed in intervals of 7 days in eachcase with a preparation of active compound at the desired applicationrate.

Evaluation is carried out 15, 19 and 25 days after the second treatment.100% means that all flies have been milled, whilst 0% means that none ofthe flies have been killed.

Active compounds, application rates and test results are shown in thetable below.

TABLE 2 Trialeurodes test Application Kill rate in % Kill rate in % Killrate in % rate of active 15 days after 19 days after 25 days aftercompound in the second the second the second Active compound g/hatreatment treatment treatment Known: Neem extract*⁾ 30 28.6 0 0 (16)Thiacloprid 100 72.8 39.5 0 According to the found calc.**⁾ foundcalc.**⁾ found calc.**⁾ invention Neem extract*⁾ 30 + {close oversizebrace} + {close oversize brace} 91.9 80.6 82.7 39.5 70.0 0 (16)Thiacloprid 100 *⁾The neem tree seed extract used is commerciallyavailable under the name Neem-Azal ® (from Trifolio). **⁾found =activity found calc. = activity calculated using Colby's formula

What is claimed is:
 1. An insecticidal and acaricidal synergisticcomposition comprising a) azadirachtin and b) abamectin, comprising aweight ratio of a) to b) of 1:0.2 to 1:60 wherein components a) and b)are present in an amount to provide synergistic results.
 2. Acomposition according to claim 1, comprising a weight ratio ofazadirachtin to abamectin of 1:0.3 to 1:60.
 3. A composition accordingto claim 1, comprising a weight ratio of azadirachtin to abamectin of1:0.3 to 1:50.
 4. A composition according to claim 1, comprising 0.5 to90% by weight of components a) and b).
 5. A method of controlling pests,comprising applying a composition according to claim 1 to the pestand/or their habitat.
 6. A method according to claim 4, wherein thepests are insects or arachnids.
 7. A process for preparing a compositionaccording to claim 1, comprising mixing a) and b) with extenders and/orsurfactants.